Radiolytic synthesis of Rh2(CO)4Cl2 and Rh6(CO)16 from RhCl3 in ethanol under CO atmosphere |
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Institution: | 1. Department of Chemistry, College of Science, Hebei Agricultural University, Baoding 071001, Hebei, China;2. College of Food Science and Technology, Hebei Agricultural University, Baoding 071001, Hebei, China |
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Abstract: | Ethanolic solutions of RhIII chloride exposed to γ-radiation under CO atmosphere are shown to be totally reduced into RhI complexes (Rh2(CO)4Cl2 and Rh(CO)2Cl-2) within a few hours with a radiolytic reduction yield of about 6.0 elementary reductions/100 eV (6.2·10-7 mol·J-1). The chloride ions freed in the medium inhibit further reduction through Rh(CO)2Cl-2 formation. On addition of copper metal under the same conditions, RhIII is transformed into Rh6(CO)16 with a conversion yield 50%. This cluster is formed via Rh2(CO)4Cl2 although Rh(CO)2Cl-2 is also present under these conditions. Rh6(CO)16 cluster is also formed under radiolysis by direct reduction of Rh2(CO)4Cl2, but metallic rhodium and other reduced products are obtained at the same time. |
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